Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF<sub>6</sub> discharge suppression

Wampler, Francis M.; Blades, Arthur T.; Kebarle, P.

doi:10.1016/1044-0305(93)85050-8

Cited by 73 publications

(50 citation statements)

References 20 publications

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“…The total ion current shows a similar voltage dependence in both positive and negative ion mode ( Figure 3a) as observed in electrospray ionization experiments [27,28]. When reaching the electrospray onset voltage (negative ion mode: -1 kV, positive ion mode: 2 kV) the total ion current starts to increase adding ions of the electrospray to the baseline current attributed to rapid evaporative ionization (REI) of the tissue [23].…”

Section: Resultssupporting

confidence: 49%

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

Guenther

Schäfer

Balog³

et al. 2011

J. Am. Soc. Mass Spectrom.

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The feasibility of electrospray (ES) ionization of aerosols generated by electrosurgical disintegration methods was investigated. Although electrosurgery itself was demonstrated to produce gaseous ions, post-ionization methods were implemented to enhance the ion yield, especially in those cases when the ion current produced by the applied electrosurgical method is not sufficient for MS analysis. Post-ionization was implemented by mounting an ES emitter onto a Venturi pump, which is used for ion transfer. The effect of various parameters including geometry, high voltage setting, flow parameters, and solvent composition was investigated in detail. Experimental setups were optimized accordingly. ES post-ionization was found to yield spectra similar to those obtained by the REIMS technique, featuring predominantly lipid-type species. Signal enhancement was 20-to 50-fold compared with electrosurgical disintegration in positive mode, while no improvement was observed in negative mode. ES post-ionization was also demonstrated to allow the detection of non-lipid type species in the electrosurgical aerosol, including drug molecules. Since the tissue specificity of the MS data was preserved in the ES post-ionization setup, feasibility of tissue identification was demonstrated using different electrosurgical methods.

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Section: Resultssupporting

confidence: 49%

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

Guenther

Schäfer

Balog³

et al. 2011

J. Am. Soc. Mass Spectrom.

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“…Experimental verification of Eqs. (1.5) and (1.6) has been provided by Smith [19], Ikonomou et al [20] and Wampler et al [21] For stable ES operation one needs to go a few hundred volts higher than the calculated V on . The electrospray onset potential is the same for both the positive and negative ion modes, but the electric discharge onset is lower when the capillary electrode is negative [19,20] and metallic.…”

Section: 24mentioning

confidence: 99%

“…The electrospray ions are observed at much lower intensities than was the case prior to the discharge, while discharge-generated ions appear with very high intensities [20,21]. Air at atmospheric pressure is not only a convenient but also a very suitable ambient gas for ES, particularly when solvents with high surface tension are to be electrosprayed.…”

Section: 24mentioning

confidence: 99%

“…In addition to the pressure effect, oxygen molecules in air have electron affinity and readily capture free electrons. Trace gases such as SF 6 , with higher electron affinity and electron capture cross sections than O 2 , can be added to assist the electron capture and suppress the electrical breakdown at higher electrospray voltages, when the atmospheric oxygen effect is insufficient [21].…”

Section: 24mentioning

confidence: 99%

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A Brief Overview of the Mechanisms Involved in Electrospray Mass Spectrometry

Kebarle

Verkerk

2009

Reactive Intermediates

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“…Anion supramolecular chemistry [20] is relatively less well developed and oftentimes anion receptors are not as strong as cation receptors in terms of thermodynamic binding constants. Moreover, negative ionization is more susceptible to corona discharge [21,22]. Therefore, negative-ion mode MS detection of noncovalent anion-receptor complexes is less common than positive-ion mode, with the examples reported [23][24][25][26][27][28] for the detection of organic explosives.…”

mentioning

confidence: 99%

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl⁻, NO₃⁻, Br⁻, and I⁻ by APCI-MS

Kavallieratos

Sabucedo

Pau

et al. 2005

J. Am. Soc. Mass Spectrom.

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As part of a mass spectrometric investigation of the binding properties of sulfonamide anion receptors, an atmospheric pressure chemical ionization mass spectrometric (APCI-MS) method involving direct infusion followed by thermal desorption was employed for identification of anionic supramolecular complexes in dichloromethane (CH 2 Cl 2 ). Specifically, the dansylamide derivative of tris(2-aminoethyl)amine (tren) (1), the chiral 1,3-benzenesulfonamide derivatives of (1R,2S)-(ϩ)-cis-1-amino-2-indanol (2), and (R)-(ϩ)-bornylamine, (3), were shown to bind halide and nitrate ions in the presence of (nϪBu) Solutions of receptors and anions in CH 2 Cl 2 were combined to form the anionic supramolecular complexes, which were subsequently introduced into the mass spectrometer via direct infusion followed by thermal desorption. The anionic supramolecular complexes Inorganic ions with small mass-to-charge ratios are typically analyzed by other techniques, such as ion chromatography and capillary electrophoresis, because under normal MS ionization conditions many compounds can produce small ions that can interfere with their detection. There are, however, some notable examples [7,8] that demonstrate the potential of soft ionization methods [9], such as atmospheric pressure chemical ionization mass spectrometry (APCI-MS) and electrospray ionization mass spectrometry (ESI-MS)[10] for analysis of inorganic ions, and ion pairs, such as ammonium nitrate [11].Increased sensitivity for MS analysis of inorganic ions has been achieved by a relatively new and promising strategy, which bridges the fields of mass spectrometry and supramolecular chemistry [12][13][14]. This approach is based on selective host molecules for specific cationic or anionic guests, which can form ionic adducts with higher molecular mass. Most of the supramolecular complexes investigated by MS involve macrocycles, such as crown ethers and cryptands, which form cationic metal-receptor complexes detectable in positive ion mode [15][16][17][18][19]. Anion supramolecular chemistry [20] is relatively less well developed and oftentimes anion receptors are not as strong as cation receptors in terms of thermodynamic binding constants. Moreover, negative ionization is more susceptible to corona discharge [21,22]. Therefore, negative-ion mode MS detection of noncovalent anion-receptor complexes is less common than positive-ion mode, with the examples reported [23][24][25][26][27][28] for the detection of organic explosives. APCI presents some advantages compared with ESI in quantitative analysis such as higher dynamic range, and is considered rugged, easy to operate, and more tolerant of higher buffer concentrations (fewer matrix effects) [31]. Multiply charged species are typically not observed in APCI-MS spectra [1]. Even though APCI is considered a soft ionization method, it has not found the same application in anion supramolecular chemistry as ESI because the larger supramolecular ions are generally not observed. Therefore, successful identification of noncova...

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Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF₆ discharge suppression

Cited by 73 publications

References 20 publications

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

A Brief Overview of the Mechanisms Involved in Electrospray Mass Spectrometry

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl⁻, NO₃⁻, Br⁻, and I⁻ by APCI-MS

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Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF6 discharge suppression

Cited by 73 publications

References 20 publications

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

Electrospray Post-Ionization Mass Spectrometry of Electrosurgical Aerosols

A Brief Overview of the Mechanisms Involved in Electrospray Mass Spectrometry

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl−, NO3−, Br−, and I− by APCI-MS

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Negative ion electrospray mass spectrometry of nucleotides: ionization from water solution with SF₆ discharge suppression

Identification of Anionic Supramolecular Complexes of Sulfonamide Receptors with Cl⁻, NO₃⁻, Br⁻, and I⁻ by APCI-MS